CN111303728A - Carbon nano tube modified polyurethane toughened epoxy resin conductive material and preparation method thereof - Google Patents
Carbon nano tube modified polyurethane toughened epoxy resin conductive material and preparation method thereof Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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Abstract
The invention relates to the technical field of epoxy resin materials, and discloses a carbon nano tube modified polyurethane toughened epoxy resin conductive material which comprises the following formula raw materials and components: the carbon nano tube grafted polyurethane prepolymer, epoxy resin, a curing agent and a defoaming agent. According to the carbon nanotube modified polyurethane toughened epoxy resin conductive material, a large number of hydroxyl groups of the carbon nanotube grafted cyclohexanehexol react with isocyanate groups of toluene diisocyanate to obtain the functionalized carbon nanotubes with isocyanate groups, polyurethane is subjected to in-situ covalent polymerization on the surface of the carbon nanotubes, and a large number of amino groups react with the terminal isocyanate groups of the carbon nanotube grafted polyurethane prepolymer simultaneously when being subjected to ring-opening crosslinking with the epoxy groups of the epoxy resin in the epoxy resin curing process of a polyamine curing agent, so that the polyurethane and the epoxy resin form a crosslinking curing network, the impact strength of an epoxy resin coating film is enhanced, and the conductivity are improved.
Description
Technical Field
The invention relates to the technical field of epoxy resin materials, in particular to a carbon nano tube modified polyurethane toughened epoxy resin conductive material and a preparation method thereof.
Background
The epoxy resin has more than two epoxy groups in molecules, can be subjected to ring-opening crosslinking with the epoxy groups by using substances containing active hydrogen such as amines and acid anhydrides, and forms a large number of network structures, has good insulating property and excellent corrosion resistance, and has various varieties, such as structural adhesives, high-temperature-resistant adhesives, foaming adhesives, latent curing adhesives, civil construction adhesives and the like, but the traditional epoxy resin material has high brittleness, low mechanical properties such as toughness and impact strength and the like, and the epoxy resin has high intrinsic resistivity and poor conductivity, so that the application range of the epoxy resin product is limited.
The carbon nano tube is formed by curling a single-layer or multi-layer graphite sheet, and the unique microstructure endows the carbon nano tube with excellent electrical property, heat conduction property and comprehensive mechanical property, so the carbon nano tube is used as a reinforcement of composite materials such as epoxy resin, polyurethane and the like to improve the comprehensive property of the materials such as the epoxy resin and the like, but the carbon nano tube has huge specific surface and high surface energy, so that the van der Waals force among carbon nano tube particles is strong, the compatibility with the epoxy resin is poor, and the formation of the carbon nano tube and the epoxy resin for improving the interface compatibility and the dispersity becomes a research hotspot.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a carbon nanotube modified polyurethane toughened epoxy resin conductive material and a preparation method thereof, which solve the problem of poor conductivity of epoxy resin and the problem of poor interface compatibility of carbon nanotubes and epoxy resin.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a carbon nano tube modified polyurethane toughened epoxy resin conductive material comprises the following raw materials and components: the carbon nano tube grafted polyurethane prepolymer, the epoxy resin, the curing agent and the defoaming agent are mixed according to the mass ratio of 5-15:100:25-35: 0.2-0.8.
Preferably, the curing agent is any one of ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine.
Preferably, the preparation method of the carbon nanotube modified polyurethane toughened epoxy resin conductive material comprises the following steps:
(1) adding an anhydrous trichloromethane solvent and a carboxylated carbon nanotube into a reaction bottle, adding thionyl chloride after uniform ultrasonic dispersion, placing the mixture into a constant-temperature oil bath reactor, heating the mixture to 50-70 ℃, uniformly stirring the mixture for reaction for 2-4 hours, carrying out reduced pressure distillation on the solution to remove the solvent, washing a solid product with anhydrous ethanol, and drying the washed solid product to prepare the acyl chlorinated carbon nanotube.
(2) Adding an anhydrous acetone solvent and the acyl chlorinated carbon nano tube into a reaction bottle, adding the inositol after uniform ultrasonic dispersion, stirring at a constant speed at 50-70 ℃ for reaction for 4-8h, washing a solid product by using absolute ethyl alcohol, and drying to prepare the polyhydroxylated carbon nano tube.
(3) Adding an N, N-dimethylformamide solvent and a polyhydroxylated carbon nanotube into a reaction bottle, adding toluene diisocyanate after uniformly dispersing by ultrasound, heating to 80-100 ℃, stirring at a constant speed for reaction for 24-48h, cooling the solution to room temperature, centrifugally separating and washing by using an ethanol solvent, and drying to prepare the isocyanated carbon nanotube.
(4) Introducing nitrogen into a reaction bottle, adding polyether glycol, toluene diisocyanate and isocyanated carbon nano-tubes, adding a catalyst dibutyltin dilaurate after uniform ultrasonic dispersion, stirring at a constant speed for reaction for 2-4h at 65-85 ℃, adding any one of a small molecular chain extender 1-4-butanediol or 1-6-hexanediol, reducing the temperature to 30-40 ℃, adding an acetone solvent to adjust the viscosity of the solution, stirring at a constant speed for reaction for 1-2h, centrifugally separating and washing by using an ethanol solvent until the upper layer liquid is clear, and preparing the carbon nano-tube grafted polyurethane prepolymer.
(5) Adding an acetone diluent, the carbon nanotube grafted polyurethane prepolymer and epoxy resin into a reaction bottle, performing a high-speed emulsification process, adding a curing agent and a defoaming agent, quickly and uniformly stirring, pouring the solution into a film forming mold, and performing thermosetting film forming to prepare the carbon nanotube modified polyurethane toughened epoxy resin conductive material.
Preferably, the constant temperature oil bath reactor in the step (1) comprises a constant temperature heating ring, an oil bath groove is arranged below the inner part of the constant temperature oil bath reactor, a supporting seat is fixedly connected to the upper part of the constant temperature oil bath reactor, a large clamping ring is fixedly connected to the lower part of the supporting seat, a large clamping groove is formed in the large clamping ring, a large clamping block is movably connected to the large clamping groove, a large regulating rod is fixedly connected to the large clamping block, a small clamping ring is movably connected to the regulating rod, a small clamping groove is formed in the small clamping ring, a small clamping block is movably connected to the small clamping groove, a small regulating rod is fixedly connected to the small clamping block, a small regulating rod is movably connected to the small regulating rod.
Preferably, the carboxyl content of the carboxylated carbon nanotubes in the step (1) is more than or equal to 3.5 percent, and the mass ratio of the carboxyl content to the thionyl chloride is 1: 80-120.
Preferably, the mass ratio of the carbon oxychloride nanotubes to the cyclohexanehexol in the step (2) is 1: 2-6.
Preferably, the mass ratio of the polyhydroxylated carbon nanotubes to the toluene diisocyanate in the step (3) is 1: 1-4.
Preferably, the mass ratio of the polyether glycol, the toluene diisocyanate, the isocyanated carbon nanotubes, the dibutyltin dilaurate and the small-molecule chain extender in the step (4) is 100:35-40:5-20:0.2-1: 3-5.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
according to the carbon nanotube modified polyurethane toughened epoxy resin conductive material, thionyl chloride reacts with carboxyl of a carboxylated carbon nanotube to obtain an acyl chlorinated carbon nanotube, an acyl chloride group reacts with hydroxyl of inositol to obtain a polyhydroxylated carbon nanotube with high hydroxylation content, a large number of hydroxyl groups of the inositol grafted by the carbon nanotube react with one isocyanate group of toluene diisocyanate to obtain a functionalized carbon nanotube with an isocyanate group, and the isocyanate group of the isocyanated carbon nanotube is used as an active center to be copolymerized with polyether diol and toluene diisocyanate, so that polyurethane is subjected to in-situ covalent polymerization on the surface of the carbon nanotube.
The carbon nanotube modified polyurethane toughened epoxy resin conductive material takes a polyamine compound as a curing agent, a large amount of amino groups react with terminal isocyanate groups of a carbon nanotube grafted polyurethane prepolymer when ring-opening crosslinking is carried out on the amino groups and epoxy groups of epoxy resin in the curing process of the epoxy resin, so that polyurethane and epoxy resin form a crosslinking curing network, carbon nanotubes and polyurethane molecular chains are introduced into an epoxy resin matrix, the mechanical properties such as toughness, impact strength and the like of an epoxy resin coating material are obviously enhanced under the synergistic action of the polyurethane molecules and the carbon nanotubes, the compatibility of the carbon nanotubes and the epoxy resin is improved through the covalent bridging action of the polyurethane molecular chains, the phenomenon that the carbon nanotubes and the epoxy resin are dispersed unevenly to form agglomeration and agglomeration is avoided, and the uniformly dispersed carbon nanotubes form a three-dimensional conductive network in the epoxy resin, the conductivity and the electric conductivity of the epoxy resin are improved.
Drawings
FIG. 1 is a schematic front view of a constant temperature oil bath reactor;
FIG. 2 is an enlarged schematic view of a large snap ring;
FIG. 3 is a schematic view of the adjustment of the base;
FIG. 4 is a scanning electron microscope TEM of isocyanated carbon nanotubes;
FIG. 5 shows an IR spectrum FT-IR of a carbon nanotube-grafted polyurethane prepolymer.
1-constant temperature oil bath reactor; 2-heating at constant temperature; 3-oil bath groove; 4-a support seat; 5-large snap ring; 6-big neck; 7-large fixture block; 8-large adjustment lever; 9-a small snap ring; 10-a mini card slot; 11-a small fixture block; 12-a small-sized adjusting rod; 13-a sliding ball; 14-a base; 15-reaction flask.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a carbon nano tube modified polyurethane toughened epoxy resin conductive material comprises the following raw materials and components: the carbon nano tube grafted polyurethane prepolymer, the epoxy resin, the curing agent and the defoaming agent are mixed according to the mass ratio of 5-15:100:25-35:0.2-0.8, and the curing agent is any one of ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine.
The preparation method of the carbon nano tube modified polyurethane toughened epoxy resin conductive material comprises the following steps:
(1) adding anhydrous trichloromethane solvent and carboxylated carbon nanotubes into a reaction bottle, wherein the carboxyl content of the carboxylated carbon nanotubes is more than or equal to 3.5 percent, adding thionyl chloride after ultrasonic dispersion is uniform, the mass ratio of the anhydrous trichloromethane solvent to the carboxylated carbon nanotubes is 1:80-120, placing the reaction bottle in a constant-temperature oil bath reactor, wherein the constant-temperature oil bath reactor comprises a constant-temperature heating ring, an oil bath groove is arranged below the inner part of the constant-temperature oil bath reactor, a supporting seat is fixedly connected above the constant-temperature oil bath reactor, a large clamping ring is fixedly connected below the supporting seat, a large clamping groove is arranged on the large clamping ring, a large clamping block is movably connected with the large clamping groove, a large adjusting rod is fixedly connected with the large clamping block, a small clamping ring is movably connected with the adjusting rod, a small clamping groove is arranged on the small clamping ring, a small adjusting rod is movably connected with the small clamping block, and arranging a reaction bottle above the base, heating to 50-70 ℃, uniformly stirring for reaction for 2-4h, distilling the solution under reduced pressure to remove the solvent, washing the solid product with absolute ethyl alcohol, and drying to prepare the carbon oxychloride nanotube.
(2) Adding an anhydrous acetone solvent and the acylchlorinated carbon nano tube into a reaction bottle, adding the cyclohexanehexol after uniform ultrasonic dispersion, wherein the mass ratio of the cyclohexanehexol to the acylchlorinated carbon nano tube is 1:2-6, reacting for 4-8h at a constant speed at 50-70 ℃, washing a solid product by using anhydrous ethanol, and drying to prepare the polyhydroxylated carbon nano tube.
(3) Adding an N, N-dimethylformamide solvent and a polyhydroxylated carbon nanotube into a reaction bottle, adding toluene diisocyanate after uniformly dispersing by ultrasound, wherein the mass ratio of the two is 1:1-4, placing the mixture into a constant-temperature oil bath reactor, heating the mixture to 80-100 ℃, uniformly stirring the mixture for reaction for 24-48h, cooling the solution to room temperature, centrifugally separating and washing the solution by using an ethanol solvent, and drying the solution to prepare the isocyanated carbon nanotube.
(4) Introducing nitrogen into a reaction bottle, adding polyether glycol, toluene diisocyanate and isocyanated carbon nano-tubes, uniformly dispersing by ultrasonic, adding a catalyst dibutyltin dilaurate, uniformly stirring and reacting for 2-4h at 65-85 ℃, adding any one of a small molecular chain extender 1-4-butanediol or 1-6-hexanediol at a constant speed, wherein the mass ratio of the two is 100:35-40:5-20:0.2-1:3-5, reducing the temperature to 30-40 ℃, adding an acetone solvent to adjust the viscosity of the solution, uniformly stirring and reacting for 1-2h, centrifugally separating and washing by using an ethanol solvent until the upper layer liquid is clear, and thus obtaining the carbon nano-tube grafted polyurethane prepolymer.
(5) Adding an acetone diluent, the carbon nanotube grafted polyurethane prepolymer and epoxy resin into a reaction bottle, performing a high-speed emulsification process, adding a curing agent and a defoaming agent, quickly and uniformly stirring, pouring the solution into a film forming mold, and performing thermosetting film forming to prepare the carbon nanotube modified polyurethane toughened epoxy resin conductive material.
Example 1
(1) Adding anhydrous trichloromethane solvent and carboxylated carbon nanotubes into a reaction bottle, wherein the carboxyl content of the carboxylated carbon nanotubes is more than or equal to 3.5 percent, adding thionyl chloride after ultrasonic dispersion is uniform, the mass ratio of the anhydrous trichloromethane solvent to the carboxylated carbon nanotubes is 1:80, placing the reactor in a constant-temperature oil bath reactor, wherein the constant-temperature oil bath reactor comprises a constant-temperature heating ring, an oil bath groove is arranged below the inner part of the constant-temperature oil bath reactor, a supporting seat is fixedly connected above the constant-temperature oil bath reactor, a large clamping ring is fixedly connected below the supporting seat, the large clamping ring is provided with a large clamping groove, the large clamping groove is movably connected with a large clamping block, the large clamping block is fixedly connected with a large adjusting rod, the adjusting rod is movably connected with a small clamping ring, the small clamping groove is movably connected with a small clamping block, the small clamping block is fixedly connected with a small adjusting rod, the small adjusting rod is, heating to 50 ℃, stirring at a constant speed for reaction for 2 hours, distilling the solution under reduced pressure to remove the solvent, washing the solid product with absolute ethyl alcohol and drying to prepare the carbon nanotube of acyl chloride.
(2) Adding an anhydrous acetone solvent and the acylchlorinated carbon nano tube into a reaction bottle, adding the cyclohexanehexol after uniform ultrasonic dispersion, wherein the mass ratio of the cyclohexanehexol to the acylchlorinated carbon nano tube is 1:2, reacting for 4 hours at a constant speed at 50 ℃, washing a solid product by using absolute ethyl alcohol, and drying to prepare the polyhydroxylated carbon nano tube.
(3) Adding an N, N-dimethylformamide solvent and a polyhydroxylated carbon nanotube into a reaction bottle, adding toluene diisocyanate after uniformly dispersing by ultrasound, placing the mixture in a constant-temperature oil bath reactor with the mass ratio of 1:1, heating to 80 ℃, uniformly stirring for reaction for 24 hours, cooling the solution to room temperature, centrifugally separating and washing by using an ethanol solvent, and drying to prepare the isocyanated carbon nanotube.
(4) Introducing nitrogen into a reaction bottle, adding polyether glycol, toluene diisocyanate and isocyanated carbon nano tubes, adding a catalyst dibutyltin dilaurate after uniform ultrasonic dispersion, stirring at a constant speed for reaction for 2 hours at 65 ℃, adding a small molecular chain extender 1-4-butanediol with the mass ratio of 100:35:5:0.2:3, cooling to 30 ℃, adding an acetone solvent to adjust the viscosity of the solution, stirring at a constant speed for reaction for 1 hour, centrifugally separating and washing by using an ethanol solvent until the upper layer liquid is clear, and preparing the carbon nano tube grafted polyurethane prepolymer.
(5) Adding an acetone diluent, the carbon nanotube grafted polyurethane prepolymer and epoxy resin into a reaction bottle, performing a high-speed emulsification process, adding a curing agent ethylenediamine and a defoaming agent in a mass ratio of 5:100:25:0.2, rapidly and uniformly stirring, pouring the solution into a film forming mold, and performing thermosetting film forming to prepare the carbon nanotube modified polyurethane toughened epoxy resin conductive material 1.
Example 2
(1) Adding anhydrous trichloromethane solvent and carboxylated carbon nanotubes into a reaction bottle, wherein the carboxyl content of the carboxylated carbon nanotubes is more than or equal to 3.5 percent, adding thionyl chloride after ultrasonic dispersion is uniform, the mass ratio of the anhydrous trichloromethane solvent to the carboxylated carbon nanotubes is 1:90, placing the reactor in a constant-temperature oil bath reactor, wherein the constant-temperature oil bath reactor comprises a constant-temperature heating ring, an oil bath groove is arranged below the inner part of the constant-temperature oil bath reactor, a supporting seat is fixedly connected above the constant-temperature oil bath reactor, a large clamping ring is fixedly connected below the supporting seat, the large clamping ring is provided with a large clamping groove, the large clamping groove is movably connected with a large clamping block, the large clamping block is fixedly connected with a large adjusting rod, the adjusting rod is movably connected with a small clamping ring, the small clamping groove is movably connected with a small clamping block, the small clamping block is fixedly connected with a small adjusting rod, the small adjusting rod is, heating to 70 ℃, stirring at a constant speed for reaction for 4 hours, distilling the solution under reduced pressure to remove the solvent, washing the solid product with absolute ethyl alcohol and drying to prepare the carbon nanotube of acyl chloride.
(2) Adding an anhydrous acetone solvent and the acylchlorinated carbon nano tube into a reaction bottle, adding the cyclohexanehexol after uniform ultrasonic dispersion, wherein the mass ratio of the cyclohexanehexol to the acylchlorinated carbon nano tube is 1:3, reacting for 6 hours at a constant speed at 70 ℃, washing a solid product by using absolute ethyl alcohol, and drying to prepare the polyhydroxylated carbon nano tube.
(3) Adding an N, N-dimethylformamide solvent and a polyhydroxylated carbon nanotube into a reaction bottle, adding toluene diisocyanate after uniformly dispersing by ultrasound, placing the mixture in a constant-temperature oil bath reactor with the mass ratio of 1:2, heating to 100 ℃, uniformly stirring for reaction for 36 hours, cooling the solution to room temperature, centrifugally separating and washing by using an ethanol solvent, and drying to prepare the isocyanated carbon nanotube.
(4) Introducing nitrogen into a reaction bottle, adding polyether glycol, toluene diisocyanate and isocyanated carbon nano-tubes, adding a catalyst dibutyltin dilaurate after uniform ultrasonic dispersion, stirring at a constant speed for reaction for 2 hours at 85 ℃, adding a small molecular chain extender 1-6-hexanediol with a mass ratio of 100:36:10:0.4:3.5, cooling to 30 ℃, adding an acetone solvent to adjust the solution viscosity, stirring at a constant speed for reaction for 1 hour, centrifugally separating and washing by using an ethanol solvent until the upper layer liquid is clear, and thus obtaining the carbon nano-tube grafted polyurethane prepolymer.
(5) Adding an acetone diluent, the carbon nano tube grafted polyurethane prepolymer and epoxy resin into a reaction bottle, performing a high-speed emulsification process, adding a curing agent triethylene tetramine and a defoaming agent, wherein the mass ratio of the triethylene tetramine to the defoaming agent is 8:100:28:0.4, quickly and uniformly stirring, pouring the solution into a film forming mold, and performing thermosetting film forming to prepare the carbon nano tube modified polyurethane toughened epoxy resin conductive material 2.
Example 3
(1) Adding anhydrous trichloromethane solvent and carboxylated carbon nanotubes into a reaction bottle, wherein the carboxyl content of the carboxylated carbon nanotubes is more than or equal to 3.5 percent, adding thionyl chloride after ultrasonic dispersion is uniform, the mass ratio of the anhydrous trichloromethane solvent to the carboxylated carbon nanotubes is 1:100, placing the reaction bottle in a constant-temperature oil bath reactor, wherein the constant-temperature oil bath reactor comprises a constant-temperature heating ring, an oil bath groove is arranged below the inner part of the constant-temperature oil bath reactor, a supporting seat is fixedly connected above the constant-temperature oil bath reactor, a large clamping ring is fixedly connected below the supporting seat, the large clamping ring is provided with a large clamping groove, the large clamping groove is movably connected with a large clamping block, the large clamping block is fixedly connected with a large adjusting rod, the adjusting rod is movably connected with a small clamping ring, the small clamping groove is movably connected with a small clamping block, the small clamping block is fixedly connected with a small adjusting rod, the small adjusting rod, heating to 60 ℃, stirring at a constant speed for reaction for 3 hours, distilling the solution under reduced pressure to remove the solvent, washing the solid product with absolute ethyl alcohol and drying to prepare the carbon nanotube of acyl chloride.
(2) Adding an anhydrous acetone solvent and the acylchlorinated carbon nanotube into a reaction bottle, adding inositol after uniform ultrasonic dispersion, wherein the mass ratio of the anhydrous acetone solvent to the acylchlorinated carbon nanotube is 1:5, reacting for 6 hours at a constant speed at 60 ℃, washing a solid product by using absolute ethyl alcohol, and drying to prepare the polyhydroxylated carbon nanotube.
(3) Adding an N, N-dimethylformamide solvent and a polyhydroxylated carbon nanotube into a reaction bottle, adding toluene diisocyanate after uniformly dispersing by ultrasound, placing the mixture in a constant-temperature oil bath reactor with the mass ratio of 1:3, heating to 90 ℃, uniformly stirring for reaction for 36 hours, cooling the solution to room temperature, centrifugally separating and washing by using an ethanol solvent, and drying to prepare the isocyanated carbon nanotube.
(4) Introducing nitrogen into a reaction bottle, adding polyether glycol, toluene diisocyanate and isocyanated carbon nano tubes, adding a catalyst dibutyltin dilaurate after uniform ultrasonic dispersion, stirring at a constant speed for reaction for 3 hours at 75 ℃, adding a small molecular chain extender 1-4-butanediol with the mass ratio of 100:38:15:0.8:4, cooling to 35 ℃, adding an acetone solvent to adjust the viscosity of the solution, stirring at a constant speed for reaction for 1.5 hours, centrifugally separating and washing by using an ethanol solvent until the upper layer liquid is clear, and preparing the carbon nano tube grafted polyurethane prepolymer.
(5) Adding an acetone diluent, the carbon nanotube grafted polyurethane prepolymer and epoxy resin into a reaction bottle, performing a high-speed emulsification process, adding a curing agent triethylene pentamine and a defoaming agent in a mass ratio of 12:100:32:0.6, quickly and uniformly stirring, pouring the solution into a film forming mold, and performing thermosetting film forming to prepare the carbon nanotube modified polyurethane toughened epoxy resin conductive material 3.
Example 4
(1) Adding anhydrous trichloromethane solvent and carboxylated carbon nanotubes into a reaction bottle, wherein the carboxyl content of the carboxylated carbon nanotubes is more than or equal to 3.5 percent, adding thionyl chloride after ultrasonic dispersion is uniform, the mass ratio of the anhydrous trichloromethane solvent to the carboxylated carbon nanotubes is 1:120, placing the reaction bottle in a constant-temperature oil bath reactor, wherein the constant-temperature oil bath reactor comprises a constant-temperature heating ring, an oil bath groove is arranged below the inner part of the constant-temperature oil bath reactor, a supporting seat is fixedly connected above the constant-temperature oil bath reactor, a large clamping ring is fixedly connected below the supporting seat, the large clamping ring is provided with a large clamping groove, the large clamping groove is movably connected with a large clamping block, the large clamping block is fixedly connected with a large adjusting rod, the adjusting rod is movably connected with a small clamping ring, the small clamping groove is movably connected with a small clamping block, the small clamping block is fixedly connected with a small adjusting rod, the small adjusting rod, heating to 70 ℃, stirring at a constant speed for reaction for 4 hours, distilling the solution under reduced pressure to remove the solvent, washing the solid product with absolute ethyl alcohol and drying to prepare the carbon nanotube of acyl chloride.
(2) Adding an anhydrous acetone solvent and the acylchlorinated carbon nano tube into a reaction bottle, adding the cyclohexanehexol after uniform ultrasonic dispersion, wherein the mass ratio of the cyclohexanehexol to the acylchlorinated carbon nano tube is 1:6, reacting for 8 hours at a constant speed at 70 ℃, washing a solid product by using absolute ethyl alcohol, and drying to prepare the polyhydroxylated carbon nano tube.
(3) Adding an N, N-dimethylformamide solvent and a polyhydroxylated carbon nanotube into a reaction bottle, adding toluene diisocyanate after uniformly dispersing by ultrasound, placing the mixture in a constant-temperature oil bath reactor with the mass ratio of 1:4, heating to 100 ℃, uniformly stirring for reaction for 48 hours, cooling the solution to room temperature, centrifugally separating and washing by using an ethanol solvent, and drying to prepare the isocyanated carbon nanotube.
(4) Introducing nitrogen into a reaction bottle, adding polyether glycol, toluene diisocyanate and isocyanated carbon nano tubes, adding a catalyst dibutyltin dilaurate after uniform ultrasonic dispersion, stirring at a constant speed for reaction for 4 hours at 85 ℃, adding a small molecular chain extender 1-6-hexanediol with a mass ratio of 100:40:20:1:5, cooling to 40 ℃, adding an acetone solvent to adjust the solution viscosity, stirring at a constant speed for reaction for 2 hours, centrifugally separating and washing by using an ethanol solvent until the upper layer liquid is clear, and preparing the carbon nano tube grafted polyurethane prepolymer.
(5) Adding an acetone diluent, the carbon nanotube grafted polyurethane prepolymer and epoxy resin into a reaction bottle, performing a high-speed emulsification process, adding a curing agent diethylenetriamine and a defoaming agent in a mass ratio of 15:100:35:0.8, rapidly and uniformly stirring, pouring the solution into a film forming mold, and performing thermosetting film forming to prepare the carbon nanotube modified polyurethane toughened epoxy resin conductive material 4.
Comparative example 1
(1) Adding anhydrous trichloromethane solvent and carboxylated carbon nanotubes into a reaction bottle, wherein the carboxyl content of the carboxylated carbon nanotubes is more than or equal to 3.5 percent, adding thionyl chloride after ultrasonic dispersion is uniform, the mass ratio of the anhydrous trichloromethane solvent to the carboxylated carbon nanotubes is 1:70, placing the reaction bottle in a constant-temperature oil bath reactor, wherein the constant-temperature oil bath reactor comprises a constant-temperature heating ring, an oil bath groove is arranged below the inner part of the constant-temperature oil bath reactor, a supporting seat is fixedly connected above the constant-temperature oil bath reactor, a large clamping ring is fixedly connected below the supporting seat, the large clamping ring is provided with a large clamping groove, the large clamping groove is movably connected with a large clamping block, the large clamping block is fixedly connected with a large adjusting rod, the adjusting rod is movably connected with a small clamping ring, the small clamping groove is movably connected with a small clamping block, the small clamping block is fixedly connected with a small adjusting rod, the small adjusting rod, heating to 70 ℃, stirring at a constant speed for reaction for 4 hours, distilling the solution under reduced pressure to remove the solvent, washing the solid product with absolute ethyl alcohol and drying to prepare the carbon nanotube of acyl chloride.
(2) Adding an anhydrous acetone solvent and the acylchlorinated carbon nano tube into a reaction bottle, adding the cyclohexanehexol after uniform ultrasonic dispersion, wherein the mass ratio of the cyclohexanehexol to the acylchlorinated carbon nano tube is 1:1, reacting for 8 hours at a constant speed at 80 ℃, washing a solid product by using absolute ethyl alcohol, and drying to prepare the polyhydroxylated carbon nano tube.
(3) Adding an N, N-dimethylformamide solvent and a polyhydroxylated carbon nanotube into a reaction bottle, adding toluene diisocyanate after uniformly dispersing by ultrasound, placing the mixture in a constant-temperature oil bath reactor with the mass ratio of 1:6, heating to 100 ℃, uniformly stirring for reaction for 48 hours, cooling the solution to room temperature, centrifugally separating and washing by using an ethanol solvent, and drying to prepare the isocyanated carbon nanotube.
(4) Introducing nitrogen into a reaction bottle, adding polyether glycol, toluene diisocyanate and isocyanated carbon nano tubes, adding a catalyst dibutyltin dilaurate after uniform ultrasonic dispersion, stirring at a constant speed for reaction for 4 hours at 85 ℃, adding a small molecular chain extender 1-6-hexanediol with a mass ratio of 100:30:25:1.2:2, cooling to 30 ℃, adding an acetone solvent to adjust the viscosity of the solution, stirring at a constant speed for reaction for 1 hour, centrifugally separating and washing by using an ethanol solvent until the upper layer liquid is clear, and preparing the carbon nano tube grafted polyurethane prepolymer.
(5) Adding an acetone diluent, the carbon nanotube grafted polyurethane prepolymer and epoxy resin into a reaction bottle, performing a high-speed emulsification process, adding a curing agent ethylenediamine and a defoaming agent in a mass ratio of 2:100:40:0.4, rapidly and uniformly stirring, pouring the solution into a film forming mold, and performing thermosetting film forming to prepare the carbon nanotube modified polyurethane toughened epoxy resin conductive contrast material 1.
The impact strength of the carbon nanotube modified polyurethane toughened epoxy resin conductive material in the examples and the comparative examples is tested by using a ZJM-06 intelligent pendulum impact tester, and the test standards are GB/T1043.1-2008 and GB/T1843-.
The electrical conductivity of the carbon nano tube modified polyurethane toughened epoxy resin conductive materials in the examples and the comparative examples is tested by using an FT-300A conductor material resistivity tester, and the test standards are GB/T1550-2018 and GB/T35494.1-2017.
In summary, according to the carbon nanotube modified polyurethane toughened epoxy resin conductive material, thionyl chloride reacts with carboxyl of a carboxylated carbon nanotube to obtain an acylchlorinated carbon nanotube, an acyl chloride group reacts with hydroxyl of cyclohexylol to obtain a polyhydroxylated carbon nanotube with high hydroxylation content, a large number of hydroxyl groups of the cyclohexylol grafted by the carbon nanotube react with an isocyanate group of toluene diisocyanate to obtain a functionalized carbon nanotube with an isocyanate group, and the isocyanate group of the isocyanated carbon nanotube is used as an active center to be copolymerized with polyether diol and toluene diisocyanate, so that polyurethane is subjected to in-situ covalent polymerization on the surface of the carbon nanotube.
Polyamine compounds are used as curing agents, during the curing process of epoxy resin, when a large amount of amino groups are subjected to ring-opening crosslinking with epoxy groups of the epoxy resin, simultaneously reacts with the terminal isocyanate group of the carbon nano tube grafted polyurethane prepolymer to form a cross-linked curing network by polyurethane and epoxy resin, introduces the carbon nano tube and the polyurethane molecular chain into an epoxy resin matrix, under the synergistic effect of polyurethane molecules and carbon nano tubes, the mechanical properties such as toughness, impact strength and the like of the epoxy resin coating material are obviously enhanced, meanwhile, the compatibility of the carbon nano tube and the epoxy resin is improved through the covalent bridging action of the polyurethane molecular chain, the phenomenon that the carbon nano tube and the epoxy resin are not uniformly dispersed to form agglomeration and reunion is avoided, the uniformly dispersed carbon nano tube forms a three-dimensional conductive network in the epoxy resin, and the conductivity and the electric conductivity of the epoxy resin are improved.
Claims (8)
1. The carbon nanotube modified polyurethane toughened epoxy resin conductive material comprises the following raw materials and components, and is characterized in that: the carbon nano tube grafted polyurethane prepolymer, the epoxy resin, the curing agent and the defoaming agent are mixed according to the mass ratio of 5-15:100:25-35: 0.2-0.8.
2. The carbon nanotube modified polyurethane toughened epoxy resin conductive material as claimed in claim 1, wherein: the curing agent is any one of ethylenediamine, diethylenetriamine, triethylene tetramine or tetraethylene pentamine.
3. The carbon nanotube modified polyurethane toughened epoxy resin conductive material as claimed in claim 1, wherein: the preparation method of the carbon nano tube modified polyurethane toughened epoxy resin conductive material comprises the following steps:
(1) adding a carboxylated carbon nanotube into an anhydrous trichloromethane solvent, adding thionyl chloride after ultrasonic dispersion is uniform, placing the mixture into a constant-temperature oil bath reactor, heating the mixture to 50-70 ℃ for reaction for 2-4 hours, and carrying out reduced pressure distillation, washing and drying to prepare an acylchlorinated carbon nanotube;
(2) adding an acylchlorinated carbon nanotube into an anhydrous acetone solvent, uniformly dispersing by ultrasonic, adding inositol, reacting for 4-8h at 50-70 ℃, filtering, washing and drying to prepare a polyhydroxylated carbon nanotube;
(3) adding a polyhydroxylated carbon nanotube into an N, N-dimethylformamide solvent, uniformly dispersing by ultrasonic waves, adding toluene diisocyanate, heating to 80-100 ℃, reacting for 24-48h, cooling, centrifugally separating, washing and drying to prepare an isocyanated carbon nanotube;
(4) in a nitrogen atmosphere, adding toluene diisocyanate and isocyanated carbon nano-tubes into polyether diol, adding a catalyst dibutyltin dilaurate after uniform ultrasonic dispersion to react for 2-4h at 65-85 ℃, adding any one of a small molecular chain extender 1-4-butanediol or 1-6-hexanediol, reducing the temperature to 30-40 ℃, adding an acetone solvent to adjust the solution viscosity, reacting for 1-2h, carrying out centrifugal separation and washing to prepare a carbon nano-tube grafted polyurethane prepolymer;
(5) adding the carbon nano tube grafted polyurethane prepolymer and epoxy resin into an acetone diluent, carrying out a high-speed emulsification process, adding a curing agent and a defoaming agent, quickly and uniformly stirring, pouring the solution into a film forming mold, and carrying out thermosetting film forming to prepare the carbon nano tube modified polyurethane toughened epoxy resin conductive material.
4. The carbon nanotube modified polyurethane toughened epoxy resin conductive material as claimed in claim 3, wherein: the constant temperature oil bath reactor in step (1) includes the constant temperature heating circle, the inside below of temperature oil bath reactor is provided with the oil bath groove, constant temperature oil bath reactor top fixedly connected with supporting seat, the big snap ring of supporting seat below fixedly connected with, big snap ring is provided with big draw-in groove, big snap ring swing joint has big fixture block, the big regulating lever of big snap ring fixedly connected with, adjust the small-size snap ring of pole swing joint, small-size snap ring is provided with small-size draw-in groove, small-size draw-in groove swing joint has small-size fixture block, the small-size regulation pole of small-size fixture block fixedly connected with, small-size regulation pole and sliding ball swing joint, sliding ball swing joint has the.
5. The carbon nanotube modified polyurethane toughened epoxy resin conductive material as claimed in claim 3, wherein: the carboxyl content of the carboxylated carbon nanotubes in the step (1) is more than or equal to 3.5 percent, and the mass ratio of the carboxyl content to the thionyl chloride is 1: 80-120.
6. The carbon nanotube modified polyurethane toughened epoxy resin conductive material as claimed in claim 3, wherein: the mass ratio of the carbon acyl chloride nanotubes to the cyclohexanehexol in the step (2) is 1: 2-6.
7. The carbon nanotube modified polyurethane toughened epoxy resin conductive material as claimed in claim 3, wherein: the mass ratio of the polyhydroxylated carbon nanotubes to the toluene diisocyanate in the step (3) is 1: 1-4.
8. The carbon nanotube modified polyurethane toughened epoxy resin conductive material as claimed in claim 3, wherein: the mass ratio of the polyether glycol, the toluene diisocyanate, the isocyanated carbon nanotube, the dibutyltin dilaurate and the micromolecular chain extender in the step (4) is 100:35-40:5-20:0.2-1: 3-5.
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